CN108707924A - Selenizing ruthenium nano particle modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, preparation method and application - Google Patents
Selenizing ruthenium nano particle modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of selenizing ruthenium nano particle modification TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, preparation method and application, selenizing ruthenium nano particle prepared by the present invention modify TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, with TiO2Nano-tube array is carrier, and deposition has equally distributed selenizing ruthenium nano particle on it, is uniformly dispersed between particle, does not have agglomeration, Electrocatalytic Activity for Hydrogen Evolution Reaction agent to expose more active site, effectively raise the activity of catalyst；Electrocatalytic Activity for Hydrogen Evolution Reaction agent prepared by the present invention has excellent Hydrogen Evolution Performance in KOH electrolyte, required overpotential is significantly lower than other base metal chalcogenide compound electrocatalytic hydrogen evolution materials, it is simple to prepare low in raw material price, synthetic method, resulting materials need not move through the electrode that subsequent processing can be used as electrocatalytic reaction, and it is with good stability, excellent electro catalytic activity is still shown after being reacted long lasting for catalytic hydrogen evolution, reusability is strong.
Description
Technical field
The present invention relates to elctro-catalyst fields, and in particular to a kind of selenizing ruthenium nano particle modification TiO2Nano-tube array
Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof, application.
Background technology
The main energy sources that traditional fossil energy is used as mankind nowadays, stockage wretched insufficiency.Meanwhile using fossil
The ecological problems such as environmental pollution, greenhouse effects caused by the energy seriously endanger the survival and development of the mankind, find green, efficient
Regenerative resource is just particularly important the existence and sustainable development of the whole mankind.Hydrogen Energy is considered most potential
New energy has many advantages, such as resource abundance, high combustion efficiency, renewable, no pollution.As the carrier of Hydrogen Energy, the life of hydrogen
Production and inventory problem are to develop and use Hydrogen Energy primary problem urgently to be resolved hurrily.But hydrogen is industrially prepared at present and still needs to consume
A large amount of fossil energy, and obtained hydrogen is impure, significantly limits the extensive use of hydrogen energy source, therefore explore sustainable
High-purity hydrogen technology of preparing to future develop and use Hydrogen Energy it is most important.
One of key reaction as water decomposition, electrocatalytic hydrogen evolution reaction are considered as one that large-scale industry prepares hydrogen
The efficient approach of kind.Currently, it is noble metal platinum that electrocatalytic hydrogen evolution, which reacts most efficient catalyst, but fancy price and relatively short
Scarce resource reserve significantly limits its extensive use in electrocatalytic hydrogen evolution field.Therefore, exploitation Cheap highly effective is stablized
Elctro-catalyst has very important significance for evolving hydrogen reaction.Although the sulfide of the transition metal such as molybdenum, tungsten, iron, cobalt, nickel,
Selenides, phosphide, carbide, nitride etc. are widely used in electrocatalytic hydrogen evolution reaction, but the performance of these catalyst is remote
Not as good as platinum-type catalyst.Although ruthenium is also noble metal, its price is only the 1/25 of platinum, helps to obtain using a small amount of ruthenium honest and clean
The efficient elctro-catalyst of valence.The ruthenium class material for being currently used in electrocatalytic hydrogen evolution reaction is mostly simple substance ruthenium nano particle, and ruthenium dosage is big,
And intergranular reunion is seriously, cannot effectively play electrocatalysis of such material in evolving hydrogen reaction.
The TiO obtained by simple anodizing2Nano-tube array has larger specific surface area and good suction
Attached ability, while may be that charge provides specific transmission channel, therefore TiO2Nano-tube array can be used for catalyst carrier
To reduce intergranular reunion, the dispersion degree of catalyst is improved, catalyst is made to expose more active sites, to improve catalysis
The activity of agent.
Based on this, the present invention provides a kind of for the insufficient improved technology scheme of the ruthenium electrocatalytic hydrogen evolution material prior art.
Invention content
It is an object of the invention to overcome the deficiencies in the prior art, it is proposed that a kind of selenizing ruthenium nano particle modification TiO2It receives
Electrocatalytic Activity for Hydrogen Evolution Reaction agent of mitron array and preparation method thereof, application.The selenizing ruthenium nano particle of the present invention modifies TiO2Nanotube
Electrocatalytic hydrogen evolution reaction of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of array suitable for alkaline electrolyte, low in raw material price, synthetic method letter
List, synthetic electro catalytic activity with good stability and excellent, reusability are strong.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of selenizing ruthenium nano particle modification TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, the Electrocatalytic Activity for Hydrogen Evolution Reaction agent are
Constituting TiO2Each TiO of nano-tube array2Homoepitaxial has selenizing ruthenium nano particle in nanotube walls.
A kind of selenizing ruthenium nano particle modification TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, institute
Preparation method is stated to include the following steps：
(1)TiO2The making of nano-tube array substrate
Titanium sheet is cut into small pieces, is taken up in order of priority to be placed in deionized water, acetone and isopropanol and is cleaned by ultrasonic, then uses height
Pure N2Drying；With NH4For the ethylene glycol solution of F as electrolyte, titanium sheet is anode, and platinized platinum is cathode, connects constant-voltage DC source,
Anodic oxidation reactions are carried out under constant-pressure conditions, wait for after reaction, taking out titanium sheet and being rinsed well with deionized water, be placed in dilute hydrochloric acid
It is ultrasonic in solution, the oxidation film of titanium plate surface is removed, high-purity N is then used2Drying；
(2)TiO2The preparation of nano-tube array
With NH4For the ethylene glycol solution of F as electrolyte, titanium sheet is anode, and platinized platinum is cathode, connects constant-voltage DC source,
Anodic oxidation reactions are carried out under constant-pressure conditions, wait for after reaction, taking out titanium sheet and being rinsed well with deionized water, high-purity N is used in combination2
Drying is subsequently placed in calcining in Muffle furnace and obtains TiO2Nano-tube array；
(3) selenizing ruthenium nano particle deposits
By RuCl3It is placed in hydrothermal reaction kettle and is uniformly mixed with selenium powder, hydrazine hydrate is added, load is then had into TiO2
The titanium sheet of nano-tube array is put into, then reaction kettle sealing is placed in thermostatic drying chamber and carries out hydro-thermal reaction, waits being reacted to certain
Time stops reaction, is cooled to room temperature, takes out titanium sheet, is rinsed repeatedly with deionized water and absolute ethyl alcohol, and natural airing；
(4) selenizing ruthenium nano particle modifies TiO2The high-temperature calcination of nano-tube array
The titanium sheet of gained is placed in tube furnace, argon gas is passed through, high-temperature calcination obtains selenizing ruthenium nano particle modification TiO2
The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array.
Selenizing ruthenium nano particle as described above modifies TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, it is excellent
It selects, in the step (1) and step (2), NH4The mass fraction of F solution is 0.15%~0.5%, water in ethylene glycol solution
Volume fraction be 0.5%~10%；
Preferably, titanium sheet is cut into thickness 0.25mm small pieces in the step (1), chip size is 1cm × 1cm.
Selenizing ruthenium nano particle as described above modifies TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, it is excellent
It selects, in the step (1) and (2), voltage needed for anodic oxidation is 20V~90V, and oxidization time is 1h~10h, and bath temperature is
10 DEG C, it is 1cm × 1cm that titanium sheet, which immerses effective area,.
Selenizing ruthenium nano particle as described above modifies TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, it is excellent
It selects, in the step (2), Muffle furnace high temperature calcination temperature is 450 DEG C, time 3h.
Selenizing ruthenium nano particle as described above modifies TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, it is excellent
It selects, in the step (3), deionized water is 35mL, RuCl in hydrothermal reaction kettle3Content is 5.18mg, and selenium powder content is 6mg.
Selenizing ruthenium nano particle as described above modifies TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, it is excellent
It selects, in the step (3), the mass fraction of hydrazine hydrate is 80%, volume 2mL.
Selenizing ruthenium nano particle as described above modifies TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, it is excellent
It selects, in the step (3), the temperature of hydro-thermal reaction is 80 DEG C~150 DEG C, and the reaction time is 4h~16h.
Selenizing ruthenium nano particle as described above modifies TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, it is excellent
It selects, in the step (4), tube furnace high-temperature calcination temperature is 400 DEG C, time 2h.
A kind of as above any selenizing ruthenium nano particle modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array is answered
With the selenizing ruthenium nano particle modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array is used for electro-catalysis in alkaline electrolyte and analyses
Hydrogen reacts.
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect：
Selenizing ruthenium nano particle prepared by the present invention modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, with TiO2Nanometer
Pipe array is carrier, and deposition has equally distributed selenizing ruthenium nano particle on it, is uniformly dispersed between particle, without agglomeration
Occur, Electrocatalytic Activity for Hydrogen Evolution Reaction agent exposes more active site, effectively raises the activity of catalyst.
There is excellent Hydrogen Evolution Performance, current density to reach in KOH electrolyte for Electrocatalytic Activity for Hydrogen Evolution Reaction agent prepared by the present invention
10mA cm-2Required overpotential is only 57mV, and Tafel slope is 50mV dec-1, hence it is evident that it is less than other base metal sulphur system
Compound electrocatalytic hydrogen evolution material.
Preparation low in raw material price, synthetic method are simple, and resulting materials need not move through subsequent processing and can be used as electro-catalysis
The electrode of reaction, and it is with good stability, still show excellent electro-catalysis after being reacted long lasting for catalytic hydrogen evolution
Activity, reusability are strong.
Description of the drawings
Fig. 1 is blank TiO2The stereoscan photograph of 1 resulting materials of nano-tube array and the embodiment of the present invention；
Fig. 2 is the energy spectrum diagram of 1 resulting materials of the embodiment of the present invention；
Fig. 3 is the transmission electron microscope photo of 1 resulting materials of the embodiment of the present invention；
Fig. 4 is the polarization curve (a) and tower of 1 resulting materials of embodiment of the present invention evolving hydrogen reaction in 1mol/l KOH solutions
Fei Er curves (b)；
Fig. 5 is polarization curve of 1 resulting materials of the embodiment of the present invention through the 1000 front and back gained of circle cyclic voltammetry scan test
(built-in figure is the current-time curvel that embodiment resulting materials are electrolysed 12 hours at overpotential 100mV).
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
The every other embodiment that logical technical staff is obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the feature in embodiment and embodiment in the present invention can be combined with each other.
Selenizing ruthenium nano particle provided by the invention modifies TiO2Nano-tube array Electrocatalytic Activity for Hydrogen Evolution Reaction agent, is closed using two-step method
At first, using anodizing with NH4The ethylene glycol solution of F is electrolyte, and high-ratio surface is formed on metal titanium sheet surface
The strong TiO of product, adsorption capacity2Nano-tube array；Then by hydro-thermal method in TiO2Selenizing ruthenium nanoparticle is deposited on nano-tube array
Son obtains selenizing ruthenium nano particle modification TiO2Nano-tube array Electrocatalytic Activity for Hydrogen Evolution Reaction agent, uses it for liberation of hydrogen in alkaline electrolyte
Reaction shows excellent electro catalytic activity and good electrochemical stability.
Embodiment 1
The selenizing ruthenium nano particle that specific embodiments of the present invention provide modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction of nano-tube array
The preparation of agent is broadly divided into four steps, is TiO first2The making of nano-tube array substrate, it is ensured that titanium sheet cleans up thoroughly,
For TiO2The formation of nano-tube array provides good basis；Followed by TiO2The anodic oxidation of nano-tube array, in metal titanium sheet
Surface forms the strong TiO of high-specific surface area, adsorption capacity2Nano-tube array；Followed by by hydro-thermal method in TiO2Nano-tube array
Upper deposition selenizing ruthenium nano particle after cleaning up, finally using high-temperature calcination, obtains selenizing ruthenium nano particle modification TiO2
Nano-tube array Electrocatalytic Activity for Hydrogen Evolution Reaction agent.It uses it for evolving hydrogen reaction in alkaline electrolyte and shows excellent electro catalytic activity and good
Good electrochemical stability.
Selenizing ruthenium nano particle modifies TiO2The preparation method of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array includes the following steps：
(1)TiO2The making of nano-tube array substrate
The titanium sheet that thickness is 0.25mm is cut into small pieces, the size effective area of small pieces is 1cm × 1cm, is taken up in order of priority
It is placed in deionized water, acetone and isopropanol and is cleaned by ultrasonic, then use high-purity N2Drying；The NH for being 0.25% with mass fraction4F、
For the ethylene glycol solution that the volume fraction of water is 2% as electrolyte, titanium sheet is anode, and platinized platinum (1cm × 1cm) is cathode, connection
Constant-voltage DC source carries out anodic oxidation reactions 1h under 60V constant-pressure conditions, and control bath temperature is 10 DEG C, is waited for after reaction,
It takes out titanium sheet to be rinsed well with deionized water, is placed in ultrasound in 0.1M dilute hydrochloric acid solutions, removes the oxidation film of titanium plate surface, then
Use high-purity N2Drying.
(2)TiO2The preparation of nano-tube array
The NH for being 0.25% with mass fraction4F, the ethylene glycol solution that the volume fraction of water is 2% is as electrolyte, titanium sheet
For anode, platinized platinum (1cm × 1cm) is cathode, connects constant-voltage DC source, anodic oxidation reactions 6h is carried out under 60V constant-pressure conditions,
Water bath with thermostatic control temperature is kept for 10 DEG C, waits for after reaction, taking out titanium sheet and being rinsed well with deionized water, high-purity N is used in combination2Drying；
It is subsequently placed in Muffle furnace, is warming up to 450 DEG C of calcining 3h, is cooled to room temperature to obtain TiO2Nano-tube array.
(3) selenizing ruthenium nano particle deposits
By 5.18mg RuCl3It is added in 35mL deionized waters with 6mg selenium powders, is uniformly mixed and 2mL mass fractions are added
For 80% hydrazine hydrate solution, 30min is persistently stirred, load is then had into TiO2The titanium sheet of nano-tube array is put into, then will be anti-
It answers kettle sealing to be placed in progress hydro-thermal reaction 12h in 120 DEG C of thermostatic drying chambers, waits for after reaction, taking out titanium sheet, using deionized water
It is rinsed repeatedly with absolute ethyl alcohol, and natural airing.
(4) selenizing ruthenium nano particle modifies TiO2The high-temperature calcination of nano-tube array
The titanium sheet of gained is placed in tube furnace, argon gas is passed through, is warming up to 400 DEG C of high-temperature calcination 2h, selenizing ruthenium is obtained and receives
Rice corpuscles modifies TiO2Nano-tube array Electrocatalytic Activity for Hydrogen Evolution Reaction agent.
Microscopic structure and performance test are carried out to the Electrocatalytic Activity for Hydrogen Evolution Reaction agent obtained by above-mentioned preparation
Using three-electrode system, TiO is modified with selenizing ruthenium nano particle2Nano-tube array is working electrode, graphite rod is
It is reference electrode to electrode, silver-silver chloride (Ag/AgCl) electrode, the KOH solution of 1mol/l is electrolyte.Before test, first
High-purity N is passed through into KOH solution2Saturation is reached, then electrode is activated by cyclic voltammetric reaction, voltage range
For -0.9V~-1.7V (vs Ag/AgCl electrodes), sweep speed 100mV/s, cycle-index 200.
Selenizing ruthenium nano particle modifies TiO2Hydrogen evolution activity of the nano-tube array electrocatalysis material in KOH passes through test pole
Change curve to be evaluated as shown in figure 4, voltage range is -0.9V~-1.7V (vs Ag/Ag Cl electrodes), sweep speed is
2mV/s。
Fig. 1 is the stereoscan photograph of 1 resulting materials of the embodiment of the present invention；Left figure is blank TiO2Nano-tube array is swept
Electromicroscopic photograph is retouched, right figure is the TiO that deposition has selenizing ruthenium nano particle2The stereoscan photograph of nano-tube array, it can be seen that
Selenizing ruthenium nano particle uniform adsorption is in TiO2Nanotube surface, without apparent agglomeration between particle.
Fig. 2 is the energy spectrum diagram of 1 resulting materials of the embodiment of the present invention；The peak of titanium, oxygen, ruthenium and selenium is shown in the power spectrum,
The atomic ratio of middle ruthenium and selenium is about 0.07: 0.23.
Fig. 3 is the transmission electron microscope photo of 1 resulting materials of the embodiment of the present invention；As can be seen from Figure 3 selenizing ruthenium nanoparticle
Sub- uniform adsorption is in TiO2Nanotube surface, without apparent agglomeration between particle, selenizing ruthenium nano particle diameter is about 19nm.
Fig. 4 is the polarization curve (a) and tower of 1 resulting materials of embodiment of the present invention evolving hydrogen reaction in 1mol/l KOH solutions
Fei Er curves (b).(a) red lines (1) are the obtained selenizing ruthenium nano particle modification TiO of the present invention in figure2Nano-tube array is black
Colo(u)r streak item (2) is commercial platinum carbon catalyst, and as can be seen from the figure material has urges with electricity similar in commercial platinum carbon catalyst
Change hydrogen evolution activity, when liberation of hydrogen current density reaches 10mA cm-2When, overpotential is only 57mV, and when overpotential is more than 150mV,
Liberation of hydrogen current density is significantly greater than commercial platinum carbon catalyst；Obtained selenizing ruthenium of the invention can be obtained according to (b) figure red lines (1)
Nanoparticle Modified TiO2The corresponding Tafel slope of nano-tube array is 50.0mV dec-1.These data are respectively less than most of
Other transition metal chalcogenide compound electrocatalysis materials, catalytic activity are higher than normal transition metal chalcogenide electro-catalysis material
Material shows that selenizing ruthenium nano particle modifies TiO2Nano-tube array has excellent electrocatalytic hydrogen evolution performance.
Fig. 5 is that selenizing ruthenium nano particle modifies TiO2The electro-catalysis stability test figure of nano-tube array；1000 from Fig. 5
Before and after circle cyclic voltammetry the comparison diagram of polarization curve can be seen that the polarization curve after 1000 circle cyclic voltammetries with just
Beginning polarization curve coincide substantially；Meanwhile under specific overpotential there is obviously current density during long-time electrocatalytic hydrogen evolution
Decaying, illustrate the present invention prepare selenizing ruthenium nano particle modification TiO2Nano-tube array Electrocatalytic Activity for Hydrogen Evolution Reaction agent has good
Electrocatalytic hydrogen evolution stability.
Embodiment 2
The time of step (2) Anodic Oxidation is 1h in the present embodiment, and resulting materials reach 10mA in liberation of hydrogen current density
cm-2When, overpotential 112mV.Other methods step is same as Example 1, and details are not described herein.
Embodiment 3
The time of step (2) Anodic Oxidation is 2h in the present embodiment, and resulting materials reach 10mA in liberation of hydrogen current density
cm-2When, overpotential 78mV.Other methods step is same as Example 1, and details are not described herein.
Embodiment 4
The time of step (2) Anodic Oxidation is 8h in this implementation, and resulting materials reach 10mA in liberation of hydrogen current density
cm-2When, overpotential 132mV.Other methods step is same as Example 1, and details are not described herein.
Embodiment 5
The time of step (2) Anodic Oxidation is 10h in the present embodiment, and resulting materials reach 10mA in liberation of hydrogen current density
cm-2When, overpotential 150mV.Other methods step is same as Example 1, and details are not described herein.
Comparative example
Comparative example is as different from Example 1：Step (1) in embodiment 1 is removed, the titanium oxide in step (2) is received
Mitron substrate is replaced with carbon cloth, and, with embodiment 1, the liberation of hydrogen current density of the elctro-catalyst finally obtained reaches 10mA for remaining
cm-2When, overpotential 137mV.
By comparative example 1-5 and comparative example it is found that selenizing ruthenium nano particle is deposited on TiOx nano by the present invention
On pipe array, it is applied in KOH alkaline electrolytes, when liberation of hydrogen current density equally reaches 10mA cm-2When, 1 Anodic of embodiment
When oxidization time is 6h, the minimum 57mV of overpotential illustrates that the preparation parameter in embodiment 1 is optimal；Carbon cloth is used in comparative example
As a contrast as substrate, under identical liberation of hydrogen current density, the more a height of 137mV of overpotential, to sum up, by selenizing ruthenium nano particle
Being deposited on contributes to reduce the overpotential needed for liberation of hydrogen on titania nanotube array, meanwhile, contribute between inhibition nano-particle
Reunion, increase electrochemical reaction active site, improve electron transport ability, therefore, obtained Electrocatalytic Activity for Hydrogen Evolution Reaction agent performance is more
It is good, there is lower overpotential.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God and principle within, any modification, equivalent replacement, improvement and so on, accompanying claims protection domain of the present invention it
It is interior.
Claims (10)
1. a kind of selenizing ruthenium nano particle modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, which is characterized in that the liberation of hydrogen electricity
Catalyst is to constitute TiO2Each TiO of nano-tube array2Homoepitaxial has selenizing ruthenium nano particle in nanotube walls.
2. a kind of selenizing ruthenium nano particle as described in claim 1 modifies TiO2The system of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array
Preparation Method, which is characterized in that the preparation method comprises the following steps：
(1)TiO2The making of nano-tube array substrate
Titanium sheet is cut into small pieces, is taken up in order of priority to be placed in deionized water, acetone and isopropanol and is cleaned by ultrasonic, then uses high-purity N2
Drying；With NH4For the ethylene glycol solution of F as electrolyte, titanium sheet is anode, and platinized platinum is cathode, connects constant-voltage DC source, constant pressure
Under the conditions of carry out anodic oxidation reactions, wait for after reaction, take out titanium sheet rinsed well with deionized water, be placed in dilute hydrochloric acid solution
Middle ultrasound removes the oxidation film of titanium plate surface, then uses high-purity N2Drying；
(2)TiO2The preparation of nano-tube array
With NH4For the ethylene glycol solution of F as electrolyte, titanium sheet is anode, and platinized platinum is cathode, connects constant-voltage DC source, constant pressure item
Anodic oxidation reactions are carried out under part, wait for after reaction, taking out titanium sheet and being rinsed well with deionized water, high-purity N is used in combination2Drying,
It is subsequently placed in calcining in Muffle furnace and obtains TiO2Nano-tube array；
(3) selenizing ruthenium nano particle deposits
By RuCl3It is placed in hydrothermal reaction kettle and is uniformly mixed with selenium powder, hydrazine hydrate is added, load is then had into TiO2Nanometer
The titanium sheet of pipe array is put into, then reaction kettle sealing is placed in thermostatic drying chamber and carries out hydro-thermal reaction, certain time to be reacted to
Stop reaction, be cooled to room temperature, takes out titanium sheet, rinsed repeatedly with deionized water and absolute ethyl alcohol, and natural airing；
(4) selenizing ruthenium nano particle modifies TiO2The high-temperature calcination of nano-tube array
The titanium sheet of gained is placed in tube furnace, argon gas is passed through, high-temperature calcination obtains selenizing ruthenium nano particle modification TiO2Nanometer
The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of pipe array.
3. selenizing ruthenium nano particle as claimed in claim 2 modifies TiO2The preparation side of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array
Method, which is characterized in that in the step (1) and step (2), NH4The mass fraction of F solution is 0.15%~0.5%, second two
The volume fraction of water is 0.5%~10% in alcoholic solution；
Preferably, titanium sheet is cut into thickness 0.25mm small pieces in the step (1), chip size is 1cm × 1cm.
4. selenizing ruthenium nano particle as claimed in claim 2 modifies TiO2The preparation side of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array
Method, which is characterized in that in the step (1) and (2), voltage needed for anodic oxidation be 20V~90V, oxidization time be 1h~
10h, bath temperature are 10 DEG C, and it is 1cm × 1cm that titanium sheet, which immerses effective area,.
5. selenizing ruthenium nano particle as claimed in claim 2 modifies TiO2The preparation side of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array
Method, which is characterized in that in the step (2), Muffle furnace high temperature calcination temperature is 450 DEG C, time 3h.
6. selenizing ruthenium nano particle as claimed in claim 2 modifies TiO2The preparation side of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array
Method, which is characterized in that in the step (3), deionized water is 35mL, RuCl in hydrothermal reaction kettle3Content is 5.18mg, selenium powder
Content is 6mg.
7. selenizing ruthenium nano particle as claimed in claim 2 modifies TiO2The preparation side of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array
Method, which is characterized in that in the step (3), the mass fraction of hydrazine hydrate is 80%, volume 2mL.
8. the selenizing ruthenium nano particle as described in claim 2 or 7 modifies TiO2The preparation of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array
Method, which is characterized in that in the step (3), the temperature of hydro-thermal reaction is 80 DEG C~150 DEG C, and the reaction time is 4h~16h.
9. selenizing ruthenium nano particle as claimed in claim 2 modifies TiO2The preparation side of the Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array
Method, which is characterized in that in the step (4), tube furnace high-temperature calcination temperature is 400 DEG C, time 2h.
10. a kind of selenizing ruthenium nano particle as described in claim 1-9 is any modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction of nano-tube array
The application of agent, which is characterized in that the selenizing ruthenium nano particle modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array is used for alkali
Property electrolyte in electrocatalytic hydrogen evolution react.
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| CN111215098A (en) * | 2020-02-19 | 2020-06-02 | 青岛科技大学 | Selenized surface-modified ruthenium dioxide nanoparticle catalyst, and preparation method and application thereof |
| CN115341233A (en) * | 2022-10-18 | 2022-11-15 | 山东华特环保科技有限公司 | High-catalysis-stability electrolytic sodium hypochlorite composite cathode and preparation method thereof |
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